General purpose monobath

ABSTRACT

A monobath composition for the combined developing and fixing of silver halide photographic emulsions comprises four developing agents, one each selected from the following classes - (a) 3pyrazolidones; (b) aminophenols; (c) dihydroxybenzenes; and (d) enediols - and a silver halide solvent. By varying the monobath temperature and the extent of agitation, the composition, without reformulation, is effective in producing satisfactory images with all film emulsions without film speed loss.

iinite States 1' tent 11 1 Kate [73] Assignee: Delaware PhotographicProduct lnc., Buffalo, NY.

[22] Filed: May 10, 1973 2'11 Appl. No.2 353,935

[52] US. Cl. 96/61 M, 96/66 R, 96/66.3 [51] Int. Cl G03c 5/38, G03c 5/30[58] Field of Search 96/61 M, 66 R, 66.3

[5 6] References Cited UNITED STATES PATENTS 2,685,515 8/1954 Wilson96/66.3 3,276,875 10/1966 Schwalenstocker.. 96/66 R 3,345,166 10/1967Land 96/61 M 3,542,554 11/1970 McMurtray..v 96/61 M 3,615,440 10/1971BIOOm 96/66-R 3,615,513 10/1971 H8181 81 8.1..... 96/61 M 3,730,7165/1973 Land 96/29 R FOREIGN PATENTS OR APPLICATIONS 765,250 1/1957 GreatBritain 96/61 M OTHER PUBLICATIONS Photo Lablndex, Morgan & Morgan, Inc.Publ., p. 3-231 3-233, I971.

Primary Examiner-Mary F. Kelley Attorney, Agent, or Firm-ClarenceA.O'Brien & Harvey B. Jacobson [57} ABSTRACT A monobath composition forthe combined developing and fixing of silver halide photographicemulsions comprises four developing agents, one each selected from thefollowing classes (a) 3-pyrazolidones; (b)

32 Claims, No Drawings BACKGROUND OF THE INVENTION 1. Field of theInvention The present invention relates to chemical compositions forthe'combined developing and fixing of silver halide photographicemulsions.

2. Description of the Prior Art Compositions for the combineddevelopingand fixing of silver halide photographic emulsions (monobaths)have conventionally employed numerous silver halide developing agents.Exemplary of these agents are l-phenyl-3-pyrazolidone (commonly calledPhenidone, a registered trademark of Ilford Ltd.), 2,4- diaminophenoldihydrochloride (Amidol), hydroquinone and ascorbic acid. In addition,various combinations of these agents are well known for use inconventional developer formulations. Thus,-for example, U.'S. Pat. No.3,276,875 teaches'the use of Phenidone in combination with each ofhydroquinone, amidol-and ascorbic acid, individually, and with a mixtureof hydroquinone and ascorbic acid. Monobaths have also employedcombinations of the various well known developing agents, as shown, forexample, in US. Pat. Nos. 2,875,048 and 2,751,300 (Phenidone-asc orbicacid), US. Pat. Nos. 3,240,603 and 3,232,761 (Phenidone-hydroquinone)and Canadian Pat. Nos. 670,962 and 682,111 (Phenidonehydroquinone andPhenidone-amidol). 1

However, every known monobath employing co mbinations of theaforementioned developers is a special purpose monobath in the sensethat its composition is formulated to make it particularly effective inthe de-.-

tory images therewith is substantially reduced. In his,

Monobath Manual at page 45, Grant Haist explains the inability of knownmonobaths to produce satisfactory results with more than one emulsion bynoting that commercial monobaths are often compromise formulations thatfail to give the best results possible with each film or paper and thatthe general-purpose monobath usually fails to please anybody but theuncritical." .7

Haist recognizes that there exists no single monobath capable ofproducing satisfactory results with all emulsions without reformulation.He suggests, at page 51, a general purpose monobath, the MM--] monobath,which supposedly produces satisfactory results with all films byadjusting the mono-bath pH for each film. While it is true that pHadjustments of the MM-l mono=bath with either sodium hydroxide orglacial acetic acid produce images having acceptable contrasts withvarious films, this can be accomplished only at the expense of speedloss. With the exception of Verichrome Pan and Royal-X Pan forwhich MM-lapparently works without adjustment, pH adjustment is accompanied byspeed losses of from ato 1 stop.

SUMMARY OFTHE INVENTION It is therefore an object of the presentinvention to provide a monobath which is effective with all films andwhich require neither reformulation nor pH adjustment to producesatisfactory images.

It is another object of-this invention to provide a monobath-compositionwhich is effective for developing and fixing all emulsions by suitablechanges in agitation and temperature.

It is still another object of this invention to provide a process ofdeveloping silver halide emulsions by employing a single monobathcomposition and varying onlyagitation and temperature for each emulsion.

Other objects and advantages will become apparent from the followingdescription and appended claims.

Briefly stated, in accordance with the aforesaid objects,'the presentinvention provides a monobath composition comprising fourdevelopingagents (a) a 3- pyrazolidone; (b) an aminophenol; (c) adihydroxybenzene; and (d) an enediol and a silver halide solvent.Preferably, the developing agents employed are Phenidone, amidol,hydroquinone and ascorbic acid, respectively, and the silver halidesolvent is sodium, potassium or ammonium thiosulfate or thiocyanate. Inanother embodiment, the present invention comprehends a process fordeveloping and fixing silver halide film by contacting the film with analkaline-monobath comprising a developing agent selected from each ofthe aforementioned classes and a silver halide solvent. By varying themonobath temperature and the extent of agitation, the monobathcompositions of the present invention are effective inproducing'satisfactory images on all film emulsions without film speedloss.

DETAILED DESCRIPTION OF THE INVENTION The present invention,in itsbroadest form, provides an alkaline monobath composition containing fourdeveloping agents and a silver halide solvent, which monobath iseffective for all films by suitable changes I in agitation andtemperature.

The silver halide developing agents employed in accordance with thepresent invention are selected, one

in which the R groups each represent various substitu-' ents such ashydrogen, alkyl or aryl groups. For example, R can be hydrogen, a groupsuch as alkyl prefera bly containing from 1 to 4 carbon atoms, or anaryl group of the benzene or naphthalene series substituted or not; andR R R and R5 can be hydrogen atoms, groups such as an alkyl grouppreferably of l to 4 carbon atoms, or an aryl group such as phenyl.

, l-phenyl-3-pyrazolidone (Phenidone) is the preferred member of the3-pyrazolidone class of agents for developing agents use in the presentinvention. Phenidone is preferred because it is commercially availablein large quantities while other known, related developing agents havingsimilar structure and characteristics are not widely available. Thefollowing compounds are representative of 3-pyrazolidone silver halidedeveloping agents which l7.l-m-acetamidophenyl-4,4-diethyl-3-pyrazolidone- 18.l-p-(B-hydroxyethylphenyl )-4,4-dimethyl-3- pyrazolidone l9. 1p-hydroxyphenyl-4,4-dimethyl-3-pyrazolidone 20. 1p-methoxyphenyl-4,4-diethyl-3-pyrazolidone 21l-p-tolyl-4,4-dimethyl-3-pyrazolidone 22.l-(7-hydroxy-2-naphthyl)-4-methyl-4-n-propyl- 3-pyrazolidone 23.l-p-diphenyl-4,4-dimethyl-3-pyrazolidone 24.l-p-(B-hydroxyethylphenyl)-3-pyrazolidone 25. 1-o-tolyl-3-pyrazolidone26. l-o-tolyl-4,4-dimethyl-3-pyrazolidone 27. 3-pyrazolidones as claimedin U.S. Pat. No.

3,284,200 of the general formula wherein Z is a divalent aliphaticgrouping which, with the carbon atoms in 4 and 5 positions of thepyrazolidone ring, completes a five-membered or membered cycloaliphaticring and R is an aryl group, e.g., phenyl or naphthyl group. Such arylgroups may be substituted with hydroxy, alkoxy, oxyalkyl, amino,substituted amino, nitro, sulphonic or carboxylic groups or halogenatoms. These compounds include, for example,1-phenyl-4,5-tetramethylene-3- pyrazolidone,l-phenyl-4,5-trimethylene-3- pyrazolidone andl-m-chlorophenyl-4,S-tetramethylene-3-pyrazolidone.

The dihydroxybenzene silver halide developing agents which are useful inthe monobath may be hydroquinone, resorcinol or pyrocatechol.

The preferred aminophenol (the term aminophenol" will be employedhereinafter as generic to amino substituted phenols, includingdiaminophenols) for use in the present invention is 2,4-diaminophenoldihydrochloride, commonly known as amidol. However, a

six-

number of aminophenol compounds can be used in place of the amide] inthe monobaths of the present invention. It will be appreciated, however,that amidol is the only member of the class that is manufactured andcommercially available in quantity. Exemplary of the aminophenol silverhalide developing agents which are useful in the present monobath arethe following:

1. p-aminophenol 2. N-methyl-p-aminophenol 3. 2,4-diaminophenol 4.2,4-diaminoresorcinol. 5. 6-methyl-2,4-diaminophenol 6.5-methyl-2,4-diaminophenol 7. 4-amino-6-methyl-2-methylaminophenol 8.6-amino-4-methyl-2-methylaminophenol 9.5-dimethylamino-2-methylaminophenol l0. 1,2,4-triaminobenzene l l.S-methyl-l ,2,4-triaminobenzene' l2. 4-hydroxy, 2,4-diaminodiphenylamine13. 4,2,4-triaminodiphenylamine l4. l,3-diamino-4,o-dihydroxybenzene Itshould also be appreciated that the acid salts of any of the foregoingaminophenol agents will likewise be suitable for use in the presentmonobaths.

The enediol silver halide developing agents which are useful in thepresent monobath include the following:

1. ascorbic acid 2. d-araboascorbic acid 3. reductic acid 4. enediols asdisclosed in U.S. Pat. Nos. 3,615,440

and represented by the formula wherein R R R and R each are selectedfrom the class consisting of hydrogen and the radical CH R wherein R ishydrogen or a monovalent organic radical, selected from the groupconsisting of amino, cyano, halo, hydroxyl, carboxyl, sulfonyl, alkyl,cycloal kyl, aryl of the benzene or naphthalene series and alkaryl ofthe benzene or naphthalene series, at least one of said R R R and Rbeing CH R Tetramethyl reductic acid is one particularly useful enediol.

5. 2-oxytetronic acid 6. 4-aryl-2-oxytetronic acid 7.4-aryl-2-oxytetronimide 8. isoascorbic acid The monobath also includes asilver halide solvent which imparts the fixing capability to thecomposition.

' Exemplary of suitable fixing agents are sodium, potassium and ammoniumthiosulfates and thiocyanates.

Inorganic sulfites, such' as sodium or potassium sulfite, are utilizedin their well-known role as preservatives for the developing agents. Inaddition, strongly basic compounds, such as sodium or potassiumhydroxide, are employed in sufficient quantity to produce an alkalinecomposition pH in the range 9.5 to 10.75. Preferably the pH is adjustedto the range 9.8 to l0.3 and most preferably to'the range It) to 10.2.The composition also includes a restrainer and grain reducer such assodium or potassium bromide.

Table 1 sets forth a broad embodiment of the monobaths of the presentinvention.

TABLE I INGREDIENT CONCENTRATION (g/I) Minimum Maximum 3-pyrazolidone l5 dihydroxybenzene 8 l4 aminophenol A. .3 enediol 1 l0 alkaline agent 37 inorganic sulfite preservative 20 75 restrainer A 2 fixing agent 60 110 In addition, conventional antifoggants, grain reducers (e.g., LiCl orNaCl), solubilizers, stabilizers, toners, buffers, antioxidants,sequestering agents and antisludge agents may be used in the monobathsof the present invention. A particularly preferred grain reducer issodium or potassium thiocyanate which may be incorporated in themonobath in amounts up to about 2 /2 grams per liter. A preferredantifoggant, which also serves as a grain reducer, is benzotriazole inminute quantities up to about 0.1 gram/liter. Whether or not ammoniumthiosulfate is employed as the fixing agent in the monobath, it has beenfound to be a useful optional additive in quantities up to 3 grams/literabove any amount used as a fixing agent to increase development speedand to yield increased density images. It is also noteworthy that wherehard water conditions prevail some flocculation may occur in themonobath. To remedy this it is desirable to include up to Zgrams of awater softener or water conditioner per liter of composition.Particularly preferred for this purpose is so dium hexametaphosphate,which may be provided as the commercially available product Calgon,manufactured by the Calgon Corporation.

A preferred form of the present invention is set forth The followingexamples are illustrative of preferred monobath compositions which have'demonstrated their effectiveness on Tri-X, Plus X, Verichrome Pan andPan-X emulsions.

EXAMPLE I Phenidone 3 g/l Hydroquinone 10 g/l Amidol 1 g/l Ascorbic Acid5 g/l NaOH 5.7 g/l N11250:; 30 g/l NaBr 1 g/l M 5 0 511,0 80 g/l Sodiumhexametaphosphate 2 g/l H;() to make 1 liter pH 10.15

When Plus-X was processed with the monobath composition of Example I itwas surprisingly observed that the film speed was increased.Specifically, density and contrast were so great that it was necessaryto decrease EXAMPLE II Phenidone 3 g/l Hydroquinone 10 g/l Amidol 1 15g/l v Ascorbic Acid 5 g/l NaOH 6 g/l Na SO- 50 g/l NaBr r g/l Na s O SHO 85 g/l Sodium hexametaphosphate 2 g/l 4)2 2 3 2 g/l Benzotriazole 0.05g/l H O to make 1 liter pH 10.25

EXAMPLE Ill Phenidone 2% g/l Hydroquinone 10 g/l Amidol 1 V2 g/lAscorbic Acid 7 -g/l NaOH v 6 g/l Na SO 30 1 g/l NaBr 0.5 g/l Na S O 5HO 80 g/l Sodium hexametaphosphate 2 g/l' KSCN 2 g/l H O to make 1 literpH 10.25

Temperature has been found to have a profound effect on the relativerates of developing and fixing with the monobaths of the presentinvention. For example, it has been noted that as the temperatureincreases above F the rate of development is greater than thecorresponding rate of fixation. However, as the temperature decreasestoward and approaches 60F, the rate of development becomes less than thecorresponding rate of fixation relative to the 70F values. While thistype of response is noted with most monobaths, with the monobath of thepresent invention the response is sufficiently profound .to enabletemperature to be effectively used as a control on monobath performance.When several monobath compositions within the scope of the inventionwere tested using Tri-X 35mm film, it was noted that thefilm showed aone to twofstop variation in density as the temperature of' the monobathvaried between 65 and F. Furthermore, when Panatomic-X 35mm film: wasprocessed using the monobath set forth in Example I, there was at leasta onefstop difference in the film when processed at 67F compared toprocessing at 75F. 5

Moreover, contrary to the generally prevailing notion tion. However, allemulsionswere found to be responsive to agitation changes. Thisobservation, together with the profound temperature effects ondevelopment and fixation rates hereinbefore described, can be com- 8Post-hardening by rinsing the developed and fixed film for about 10-30seconds with either an acid alum hardener or an aldehyde was found toyield excellent results, as shown in the following Examples whichillustrate the use of exemplary hardener rinse solutions.

not only with the monobath of the present invention but with allmonobaths. Not only does post-hardening give good hardening but itneither reduces emulsion speed nor decreases monobath shelf life.

bined to advantage in utilizing the monobaths of the present inventionwith all known emulsion films with- EXAMPLE Iv but need to adjust pH orto reformulate for each emulsion. I

To establish applicable temperature and agitation pa- Ringgi Potassiumsulfate 2 g rameters for various emulsions a number of. monobath SodiumBisulfate 5 g compositions within the scope of the invention were g f gggg g tested under various conditions on 35mm Tri-X, Plus- X, VerichromePan and Pan-X and on 120 Tri-X, Plus- X and Pan-X. Table lll sets'forththe optimum process- EXAMPLE V ing temperature and time for eachemulsion with the Exemplary ofa post-hardener concentrate is thefolmonobaths of the present invention to achieveresults lowingcomposition similar to D-76 conventional development in terms ofcontrast and density range. In addition, Table Ill sets 88% Ethanolamine140 g forth mean agitation modes for optimum performance fllcxid t A d138 g of the monobaths with each emulsion. It w ll be apprefi a g g 80 gciated that the agitation modes are not rigorous, un- Ethylene Glycol gvarying criteria, but rather are guidelines which, if followed withinabout a 20 percent permissible variation, One ounce of the post-hardenerconcentrate diluted will yield consistently satisfactory results. withwater makes 1 quart of rinse solution.

TABLE III FlLM FOR- TEMPERA- AGlTATlON TOTAL MAT TURE DEVELOP.

TIME

TRI x mm 68-70F 60sec then s sec/30sec 6 min. PLUS X 35mm 586lF 10 set:then 5 sec/60sec 6Vz-7 min. VER PAN 35mm 66-68F l5 sec then 5 sec/30sec6 min. PAN X 35mm 7072F continuous 6 min. TRl X 120 6769F 30 sec then 5sec/305cc 7 min. PLUS X 120 58-.6lF 10 sec then 5 sec/60sec 7% min. PANX 120 oil-70F continuous 7 min.

Emulsion hardening when processing with mono- EXAMPLE/V1 baths hasheretofore taken the form'of (a) prehardening the emulsion in ahardening solution, or (b) incor 85% glutaraldehyde 10 ml porating ahardener in the monobath. Neither tech- 40 z o e 1 liter nique has beenfound to be satisfactory. Prehardening is itself time consuming,requiring, for example, 90 seconds using the solution of U.S. Pat. No.Re. 26,601. In A glutaraldehyde post-hardener is effective but suffersaddition, following prehardening a thorough rinsing is from the problemthat it ages at a muchfa'ster rate than necessary to avoid prehardenercarry-over into the other post-hardeners, which may last for years.monobath and contamination of'the monobath. Incor- It should beappreciated that the post-hardening soluporation ofa hardener into amonobath, whether by detions of Examples IV-Vl are merely illustrativeof the sign or through inadvertence, as by carry-over, typinumeroushardening solutions which are suitable. For cally causes a loss ofemulsion speed and shortens the example, virtually any knownprehardening solution shelf life of the monobath. For example, uponincorcan also be used for post-hardening. In addition, known poration ofan aldehyde hardener in a monobath a pH and temperature conditions forprehardening are slight discoloration of the monobath evidences aninalso satisfactory for post-hardening. creased rate of monobathoxidation with an attendant A particular advantage of the monobathcomposiloss in development capability. Moreover, break downtions of thepresent invention is the flexibility they of the aldehyde hardeneritself in the monobath makes allow in commercial packagingconfigurations to insure it doubtful whether effective hardening can beprolonged shelf life. For example, in one embodiment achieved,particularly where the monobath is prepared the primary monobathingredients, except for the alkaand kept on the shelffor 3 to 6 months.linity agent and the four developers, are provided in dry It has beenfound, contrary to some reported obserpowdered form. The alkalinityagent is a separately vations (see, Sasai and Mil, Studies onPhotographic packaged aqueous concentrate and the developers areMonobaths Containing Posassium Thiocyanate, Photoprovided in powdered,pre-mixed form in a number of graphic Science and Engineering, Volume 8,No. 3, individual compartments, each compartment containpages 270-2751964), that hardening following develing sufficient developer toactivate, for example, 16 opment and fixation, i.e., post-hardening, iseffective, ounces of monobath solution. To use such a configuration, thepowdered primary ingredients are dissolved in about 48 ounces of waterat 52C to form a concentrate having a shelf life in a tightly stopperedbottle of at least one year. To prepare and activate the monobath, the

TABLE 'IV NaOH aqueous concentrate. BASIC MIX 1 21. Sodium Sulfite 11.Sodium Bromide Base Mix 0. Sodium Thiosulfate Y d. Ascorbic Acid e.Amidol f. Hydroquinone g. Phenidone Base Mix Z Various configurations ofthe ingredients of Table IV are possible to contribute to the longevityof the packaged ingredients and assure freshness of the product to theultimate user.

CONFIGURATION 1 The NaOH concentrate is added to 800 mls H O. Basic mix(2) is then added and when dissolved additional water is added to make 1liter. Alternatively, Basic Mix (2) may beadded in increments toactivate only a portion of the diluted NaOh concentrate. CONFIGURATION 2t --The NaOh concentrate is added to 800 mls H O. Base mix (2) Y is thenadded and'the resultant solution stored'prior to use at which time it isactivated by add ing Base mix (2') Z and H to make 1 liter.Alternatively, Base mix (2) Z may be added in increments to activateonly a portion of the stored solution. CONFIGURATION 3 l The NaOhconcentrate is added to 800 mls of H 0. Base mix (2) Y and ingredient(2)(d) are then added and the resultant solution is stored prior to useat which time it is activated by adding ingredients (2)(e) (2)(f) and(2)(g).and H O to make 1 liter. Alternatively, ingredients 2)(e),(2)(f), and (2)(g) may be added in increments to activate only a portionof the stored solutlon. CONFIGURATION 4 The NaOh concentrate is added to800 mls H O. Base mix (2) Y plus ingredients (2)(d) and (2)(g) are thenadded and the resultant solution is stored prior to use at which time itis activated by adding ingredients (2)(e) and (2)(f) to the solution andH 0 to make 1 liter. Alternatively, ingredients (2((e) and (2)(1) may beadded in increments to activate only a portion of the stored solution.

Thus the method, composition and packaging of this monobath provide aphotographic worker with: (1) a monobath that produces a maximum ofshadow detail and full emulsion speed; (2) a primary aqueous mixturethat has a shelf life of at least six months to one year prior toactivationjand- (3) a methodof activation that enables the worker toactivate the solution only when he needs to process film ensuring afresh solution. By varying temperature and agitation it is possible toprocess all commercially available camera films intended Ill forcontinuous tone photography without the need of pH adjustment orreformulating the monobath due to the inherent differences betweendifferent speed films.

While the present invention has been described with referencetoparticular embodiments thereof, it will be understood that numerousmodifications can be made by those skilled in the art without actuallydeparting from the scope of the invention. Accordingly, allmodifications and equivalents may be resorted to which fall within thescope of the invention as claimed.

What is claimed 'as new is as follows:

I. An aqueous composition for the combined developing and fixing ofexposed silver halide photographic emulsions,.having a pH in the range9.5 10.75, comprising the following ingredients in the weight proportionranges indicated per liter of composition:

3-pyraz0lidone developer 1 to 5 grams.

8 to 14 grams,

% to 3 grams.

Enediol developer selected from the groupconsisting of ascorbic acid,d-araboascorbic acid, reductic acid, 2- ozytetronic acid,4-aryl-2ozytetronic acid, .l-aryl?- ozytetronimidc. isoascorbic acid'andcnediols having the chemical structure represented by the formulawherein R R R and R are selected from the group consisting of hydrogenand the radical CH;R R is selected from hydrogen and a monovalcntradical selected from the group consisting of amino, cyano,

halo, hgrtraryl, carboxyl, sul/on alkyl, c'ycloalh l.

aryl of the benzene 0r naphthalene series and alkaryl o/the benzene ornaphthalene series, at least one 0] said R R R and R4 being the radicalCH R Inorganic sulfite preservative 20 to grains.

Alkaline agent 1 to 10 grams 3 to 7 grams.

Restrainer 4 to 2 grams.

Fixing agent selected from sodium, potassium and 60lo grams.

ammonium thzosulfates and thincganmes.

2. A composition, as claimed' in claim 1, wherein said 3-pyrazolidonedeveloper is selected from developing agents having the followingchemical structure:

wherein R R R R and R are selected from hydrogen, alkyl groupscontaining from 1 to 4 carbon atoms and aryl groups selected from thebenzene and naphthalene series.

3. A composition, as claimed in claim 2, wherein said 3-pyrazolidone isl-phenyl-3-pyrazolidone.

4. A composition, as claimed in claim 1, wherein said enediol isselected from tetramethyl reduction acid and ascorbic acid. i

5. A composition, as claimed in claim 1, wherein said 11 aminophenoldeveloper is 2,4-diaminophenol dihydrochloride. I I

6. A composition, as claimed in claim 1, comprising the followingingredients in the weight proportion ranges indicated per literofcomposition:

3pyrazolidone developer 2 to 4 grams dihydroxybenzene developer 8 to l2grams aminophenol developer V: to 2 grams enediol developer 3 to 7 gramsinorganic sulfite preservative 20 to 75 grams alkaline agent 3 to 7grams restrainer A to 1% grams fixing agent 70 to.95 grams.

7. A composition, as claimed in claim 1, wherein said dihydroxybenzeneis hydroquinone, said 3- pyrazolidone is l-phenyl-3-pyrazolidone, saidenediol is selected from the group consisting of tetramethyl reducticacid and ascorbic acid, and said aminophenolis 2,4-diaminophenoldihydrochloride.

8. A composition, as claimed in claim 7, wherein said inorganic sulfitepreservative is selected from sodium and potassium sulfite.

9. A composition, as claimed in claim 7, wherein said alkaline agent isselected from sodium and potassium hydroxide.

10. A composition, as claimed in claim 7, wherein said restrainer isselected from sodium and potassium bromide.

11. A composition, as claimed in claim 7, wherein said pH is in therange 9.8 10.3

12. A composition, as claimed in claim 7, further including at least oneof the following additional ingredients: I

a. up to We grams perliter of a grain reducer selected from sodium andpotassium thiocyanate;

b. up to 0.1 gram per liter of benzotriazole;

c. up to 3 grams per liter of ammonium thiosulfate;

and cl. up to 2 grams per liter of a water softening agent.

13. A composition, as claimed in claim 12, wherein said additionalingredient is a grain reducer selected from sodium and potassiumthiocyanate.

14. A composition, as claimed in claim 12, wherein said additionalingredient is benzotriazole.

15. A composition, as claimed inclaim 12, wherein said additionalingredient is ammonium thiosulfate.

16. A composition, as claimed in claim 12, wherein said additionalingredient is a water softening agent.

17. A composition, as claimed in claim 15, wherein said water softeningagent is sodium hexametaphos- 18. An aqueous compositionfor the combineddeveloping and fixing of exposed silver halide photographic emulsionscomprising the following ingredients in the weight proportions indicatedper liter of composition:

l'-phenyl- S-pyrazolidone 3 grams Hydroquinone 10 grams Amidol 1 gramAscorbic Acid 5 grams Na SO 30 grams NaOH 5.7 grams NaBr 1 gram Na s o80 grams Sodium hexametaphosphate grams.

'19. A process for simultaneously. developing and fixing an imagewiseexposed silver halide emulsion com- 'dihydroxybenzene prising contactingsaid emulsion with an aqueous monobath composition having a pH 'in therange of 8 9.5, said monobath comprising the following ingredients inthe weight proportion ranges indicated per liter of composition:

3-pyrazolid0ne developer 1 to 5 grams.

8 to 14 grams.

% to 3 grams.

Enediol developer selected from the group consisting of ascorbic acid,darab0ascorbic acid, reduetic acid, 2- orytetronic acid,.l-aryl-E-oxyletronic acid, .l-aryl-Q- oz letronimide, isoascorbic acidand cnediOZ-y having the chemical structure represented by the formulawherein R R R and R are selected from the group consisting of hydrogenand the radical C[IgR, R is selected from hydrogen and a monovalerzlradical selected from the group consisting of amino, cg arzo. halo,hyaroayl, carhoxyl, suljonyl, alkyl, cgclunlkgl. arr/l of the hcnlcne ornaphlhalcnrseries and (ll/illl'j/l aflhe benzene or naphthalene series,at least Ill)! 0] said R H It and R4 being the radical CII I\;,.

1 to 10 grains lnorganic sullito preservative... 20 to grams.

Alkaline agent o 3107 grams.

Reslraincr to 2 grams.

Fixing agentselectcd from sodium, potassium and 60 to grams. am noniurnthiosul/ates and thiocyanates.

20. A process, as claimed in claim 19, wherein said 3-pyrazolidonedeveloper is selected from developing agents having the followingchemical structure:

wherein R R R R and R are selected from hydrogen, alkyl groupscontaining from 1 to 4 carbon atoms and aryl groups selected from thebenzene and naphthalene series.

21. A process, as claimed in claim 19, wherein said is hydroquinone,said 3- pyrazolidone is l-phenyl-3-pyrazolidone, said enediol isselected'from the group consisting of tetramethyl reductic acid andascorbic-acid and said aminophenol is 2,4-diaminophenol dihydrochloride.

22. A process, as claimed in claim 21, wherein said pH is in the range9.8 10.3.

23. A process, as claimed in claim 21, further including at least one ofthe following additional ingredients: a. up to 2% grams per liter'of agrain reducer selected from sodium and potassium thiocyanate;

b. up to 0.1 gram per liter of benzotriazole;

c. up to 3 grams per liter of ammonium thiosulfate;

and

d. up to 2 grams per liter of a water softening agent.

24. A process, as claimed in claim 23, wherein said l-phenyl-3-pyrazolidone 3 grams Hydroquinone 10 grams Amidol 1 gram Ascorbic Acid5 grams Na SO 30 grams NaOl-l 5.7 grams NaBr v 1 gram Na s O SH O 88grams Sodium Hexametaphosphate grams.

25. A process, as claimed in claim l9, further including the step ofagitating said monobath to said emulsion. l

26. A process,'as claimed in claim 25, wherein said monobath temperatureis in the range 60 72F.

27. A process, as claimed in claim 19, further including the step ofrinsing the developed and fixed emulsion in an aqueous hardening bath.

28. A process, as claimed in claim 27, wherein sai hardening bathincludes a silver halide emulsion hardener selected from acid alum andaldehyde hardeners.

29. A process, as claimed in claim 28, wherein said hardening bathcomprises the following ingredients in the weight proportions indicatedper liter of hardening bath:

Boric acid 5 grams Aluminum potassium sulfate 5 grams Sodium bisulfate 5grams.

30. A dry mixture, all ingredients of which are adapted to be admixedand dissolved in water to pro- A dihydroxybenzene developer selectedfrom the group consisting of hydroquinone, resorcinol and pyrocatechol;

An amlnophenol developer selected from the group consisting ofnominaphenol, N-methyl-p-aminophenol, 2,4-dianzinphenol,2,4-diamin0resorinethyl-Q-methglaminophenol,(Lamina-441ieihyl-2-meihylaminophenol, 5-dimeihylamin02-1):ethylaminophenol, l.24,-lriaminoherzzene, a-meih I-1,2,4-triarninobenzene, .l-hgdroag, 2,.i-diaminodiphch lamina,4,2,4-lriraininofdiphenylamine, 1,3-diarnina-4,T-aihgdroxybenzene, andthe acid sails ereo An enediol developer selected from the groupconsisting of ascorbic acid, d-arabaascorbic acid, reductz'c acid,Z-ozytetronic acid, ,4-aryl-2-olgietronic acid, l-argl-B-orgtetrOnimide,isoascorbic acid and enediols having the chemical structure representedby the formula A fixing agent selected from sodium; potassium andammonium thiosulfates and thiecganatcs. V

31. A dry mixture, as claimed in claim 30, wherein said dihydroxybenzenevis hydroquinone, said 3-/ pyrazolidone is l-phenyl-3-pyrazolidone, saidenediol is selected from thegroup consisting of tetramethyl reducticacid and ascorbic acid and said aminophenol .is

2,4-diaminophenol dihydrochloride.

.32. A process, as claimed'in claim 27, wherein said hardening bathcomprises the-following ingredients in the weight proportions indicatedper liter of hardening bath:

88% Ethanolamine 140 grams Boricacid grams Glacial acetic acid 140 gramsAluminum chloride 6H O grams Ethylene glycol 30 grams.

1. AN AQUEOUS COMPOSITION FOR THE COMBINED DEVELOPING AND FIXING OFEXPOSED SILVER HALIDE PHOTOGRAPHIC EMULSIONS, HAVING A PH IN THE RANGE9.5 - 10.75, COMPRISING THE FOLLOWING INGREDIENTS IN THE WEIGHTPROPORTION RANGES INDICATED PER LITER OF COMPOSITION:
 2. A composition,as claimed in claim 1, wherein said 3-pyrazolidone developer is selectedfrom developing agents having the following chemical structure:
 3. Acomposition, as claimed in claim 2, wherein said 3-pyrazolidone is1-phenyl-3-pyrazolidone.
 4. A composition, as claimed in claim 1,wherein said enediol is selected from tetramethyl reduction acid andascorbic acid.
 5. A composition, as claimed in claim 1, wherein saidaminophenol developer is 2,4-diaminophenol dihydrochloride.
 6. Acomposition, as claimed in claim 1, comprising the following ingredientsin the weight proportion ranges indicated per liter of composition:
 7. Acomposition, as claimed in claim 1, wherein said dihydroxybenzene ishydroquinone, said 3-pyrazolidone is 1-phenyl-3-pyrazolidone, saidenediol is selected from the group consisting of tetramethyl reducticacid and ascorbic acid, and said aminophenol is 2,4-diaminophenoldihydrochloride.
 8. A COMPOSITION, AS CLAIMED IN CLAIM 7, WHEREIN SAIDALKAGANIC SULFITE PRESERVATIVE IS SELECTED FROM SODIUM AND POTASSIUMSULFITE.
 9. A COMPOSITION, AS CLAIMED IN CLAIM 7, WHEREIN SAID ALKALINEAGENT IS SELECTED FROM SODIUM AND POTASSIUM HYDROXIDE.
 10. Acomposition, as claimed in claim 7, wherein said restrainer is selectedfrom sodium and potassium bromide.
 11. A composition, as claimed inclaim 7, wherein said pH is in the range 9.8 - 10.3
 12. A composition,as claimed in claim 7, further including at least one of the followingadditional ingredients: a. up to 1 1/2 grams per liter of a grainreducer selected from sodium and potassium thiOcyanate; b. up to 0.1gram per liter of benzotriazole; c. up to 3 grams per liter of ammoniumthiosulfate; and d. up to 2 grams per liter of a water softening agent.13. A composition, as claimed in claim 12, wherein said additionalingredient is a grain reducer selected from sodium and potassiumthiocyanate.
 14. A composition, as claimed in claim 12, wherein saidadditional ingredient is benzotriazole.
 15. A composition, as claimed inclaim 12, wherein said additional ingredient is ammonium thiosulfate.16. A composition, as claimed in claim 12, wherein said additionalingredient is a water softening agent.
 17. A composition, as claimed inclaim 15, wherein said water softening agent is sodiumhexametaphosphate.
 18. An aqueous composition for the combineddeveloping and fixing of exposed silver halide photographic emulsionscomprising the following ingredients in the weight proportions indicatedper liter of composition:
 19. A process for simultaneously developingand fixing an imagewise exposed silver halide emulsion comprisingcontacting said emulsion with an aqueous monobath composition having apH in the range of 8 - 9.5, said monobath comprising the followingingredients in the weight proportion ranges indicated per liter ofcomposition:
 20. A process, as claimed in claim 19, wherein said3-pyrazolidone developer is selected from developing agents having thefollowing chemical structure:
 21. A process, as claimed in claim 19,wherein said dihydroxybenzene is hydroquinone, said 3-pyrazolidone is1-phenyl-3-pyrazolidone, said enediol is selected from the groupconsisting of tetramethyl reductic acid and ascorbic acid and saidaminophenol is 2,4-diaminophenol dihydrochloride.
 22. A process, asclaimed in claim 21, wherein said pH is in the range 9.8 - 10.3.
 23. Aprocess, as claimed in claim 21, further including at least one of thefollowing additional ingredients: a. up to 2 1/2 grams per liter of agrain reducer selected from sodium and potassium thiocyanate; b. up to0.1 gram per liter of benzotriazole; c. up to 3 grams per liter ofammonium thiosulfate; and d. up to 2 grams per liter of a watersoftening agent.
 24. A process, as claimed in claim 23, wherein saidmonobath composition comprises the following ingredients in the weightproportions indicated per liter of composition:
 25. A process, asclaimed in claim 19, further including the step of agitating saidmonobath to said emulsion.
 26. A process, as claimed in claim 25,wherein said monobath temperature is in the range 60* - 72*F.
 27. Aprocess, as claimed in claim 19, further including the step of rinsingthe developed and fixed emulsion in an aqueous hardening bath.
 28. Aprocess, as claimed in claim 27, wherein said hardening bath includes asilver halide emulsion hardener selected from acid alum and aldehydehardeners.
 29. A process, as claimed in claim 28, wherein said hardeningbath comprises the fOllowing ingredients in the weight proportionsindicated per liter of hardening bath:
 30. A dry mixture, allingredients of which are adapted to be admixed and dissolved in water toproduce a solution having a pH in the range 9.5 to 10.75 for thecombined developing and fixing of an exposed silver halide photographicemulsion comprising:
 31. A dry mixture, as claimed in claim 30, whereinsaid dihydroxybenzene is hydroquinone, said 3-pyrazolidone is1-phenyl-3-pyrazolidone, said enediol is selected from the groupconsisting of tetramethyl reductic acid and ascorbic acid and saidaminophenol is 2,4-diaminophenol dihydrochloride.
 32. A process, asclaimed in claim 27, wherein said hardening bath comprises the followingingredients in the weight proportions indicated per liter of hardeningbath: